Hair dye and hair-dyeing methods using the same

ABSTRACT

A hair dye and hair-dyeing methods using the hair dye are provided. The hair dye comprises, as essential ingredients, (i) a formulation primarily composed of a dye component including indican derived from indigo plants and (ii) a formulation primarily composed of a β-glucosidase enzyme component. Hair is first mordanted with a dye mordant such as aluminum, iron and the like, and then secondly the prepared hair dye is uniformly applied to the hair either directly or as a mixture of the dye and a proper amount of water. Upon completion of the hair-dyeing, hair is rinsed with water and is finished by drying.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention generally relates to hair dyes and, moreparticularly, to a new hair dye using a fresh natural indigo leaf or ajuice of a fresh natural indigo leaf. The present invention also relatesto a method for dyeing hair using such dyes.

2. Description of the Prior Art

Conventionally, several compositions and methods for dyeing hair havebeen known. Examples of such a known hair dyeing dye include asynthesized hair dye using an oxidation dye which have a highhair-dyeing performance as well as a long-lasting performance, aplant-based hair dye which contains “henna” as its primary component andis widely used in Europe and in the US, and a hair dye commonly referredto as “hair manicure”, to which an acid dye is blended.

Each of the known hair dyes is associated with certain drawbacks.Oxidation dyes are known to cause allergies in humans. The “henna” dyehas a limited variation in color and does not go well with the blackhair of the Japanese. Some allergic events are also reported for thedye. Acid dyes have a low durability since the dyes are just soaked upby the hair. Some of the conventional hair-dyeing agents are known tostain skin when spilt onto skin.

A hair dye is proposed in Japanese Patent Laid-open Publication No. Hei10-53720 which is made by emulsifying or suspending a powderedplant-based dye together with liquid silicone, paraffins, a plant oranimal oil using a surfactant or the like. Though this hair dye has animproved agent stability as well as an enhanced functionality in termsof hair-dyeing operation, it has a relatively low hair-dyeingperformance, a property which should be prioritized for a hair dye.Thus, this hair dye does not meet all of the requirements either.

The indigo plant has long been grown by mankind and has a long historyof being used as a dye for dyeing fibers, a coloring agent for food, ora medicament such as a detoxifying agent or an antipyretic agent. Makinguse of the dye component of the indigo in dyeing hair may provide thosewho are sensitive to conventional hair dyes with the benefit of dyeingtheir hair without having troubles. Furthermore, the indigo dyes arefree of irritation and damage to scalps and hair and give hair body anda new texture of hair, providing a hair-dyeing effect that suits haircolor of the Japanese.

SUMMARY OF THE INVENTION

The present invention addresses the above-mentioned problem.Accordingly, it is a first object of the present invention to provide anew hair dye using a natural indigo plant which does not stain skinswhen spilt thereon and is, for example, capable of preventing white hairfrom turning yellowish and of dyeing hair with natural tone while hidingwhite hair and which provides long-lasting, durable colors. A secondobject of the present invention is to provide a hair-dyeing method ofdyeing hair using such new hair dyes.

The hair dye according to the first aspect of the present invention usesindigo dyes, which have a long history of being used as dyestuff forfibers, for the purpose of dyeing hair. The dye has an excellent shelfstability, does not stain skins when spilt, and provides long-lasting,durable colors. The dye is advantageous in that it allows the people whoare sensitive to conventional hair dyes and could not dye their hair toenjoy dyeing their hair. The dye is free of irritation and damage toscalps and hair and is capable of preventing white hair from turningyellowish and of providing hair with natural tone. Also, the dyeprovides hair with a new textile and provides a long-lasting color thatsuits the hair color of the Japanese.

In order to attain the above-mentioned objects, a first aspect of thepresent invention is a new hair dye comprising, as essentialingredients, (i) a formulation primarily composed of a dye componentincluding indican derived from an indigo plant and (ii) a formulationprimarily composed of a β-glucosidase enzyme component.

The hair dye according to the first aspect of the present invention usesindigo dyes, which have a long history of being used as dyestuff forfibers, for the purpose of dyeing hair. The dye has an excellent shelfstability, does not stain skins when spilt, and provides long-lasting,durable colors. The dye is advantageous in that it allows the people whoare sensitive to conventional hair dyes and could not dye their hair toenjoy dyeing their hair. The dye is free of irritation and damage toscalps and hair and is capable of preventing white hair from turningyellowish and of providing hair with natural tone. Also, the dyeprovides hair with a new textile and provides a long-lasting color thatsuits the hair color of the Japanese.

A second aspect of the present invention is characterized in that, inthe foregoing hair dye, the formulation (i) primarily composed of thedye component including indican derived from an indigo plant is oneselected from the group consisting of a fresh indigo leaf β-glucosidaseof which is inactivated, an extract solution which contains indicanextracted from fresh indigo leaves and which has its β-glucosidasecomponent inactivated, an indican-containing powder obtained byfreeze-drying the indican-containing extract solution, anindican-containing formulation in which the fresh indigo leaves havingtheir β-glucosidase component inactivated and/or the indican-containingextract solution and/or the indican-containing powder is carried by acarrier such as starch, cellulose, and silk powder, and a mixturethereof.

The hair dye according to the second aspect of the present invention,which uses the formulation (i) which is not only highly stable but canalso be obtained easily and economically, has the same advantages as thehair dye according to the first aspect of the present invention. The dyehas a further advantage that it can be manufactured more easily andeconomically.

A third aspect of the present invention is characterized in that, in theforegoing hair dye, the formulation (ii) primarily composed of theβ-glucosidase enzyme component is one selected from the group consistingof a fresh indigo leaf, Enokitake (Flammulina velutipes), Shiitake(Lentinus Edodes), a young corn leaf, an apricot kernel, an almond, aβ-glucosidase-containing extract solution extracted therefrom, and amixture thereof.

The hair dye according to the third aspect of the present invention,which uses the formulation (ii) which is not only highly stable but canalso be obtained easily and economically, has the same advantages as thehair dye according to the first aspect of the present invention. The dyehas a further advantage that it can be manufactured more easily andeconomically.

A fourth aspect of the present invention Is characterized in that, inthe foregoing hair dye, the formulation (ii) primarily composed of theβ-glucosidase enzyme component is one selected from the group consistingof a juice of a fresh indigo leaf, a β-glucosidase-containing powderobtained by freeze-dried fresh indigo leaves or juice thereof, and amixture thereof.

The hair dye according to the fourth aspect of the present invention,which uses the component (ii) which is not only highly stable but canalso be obtained easily and economically, has the same advantages as thehair dye according to the first aspect of the present invention. The dyehas a further advantage that it can be manufactured more easily andeconomically.

A fifth aspect of the present invention is characterized in that, theforegoing hair dye further comprises another dye material selected fromthe group consisting of a natural plant dyestuff of gamene, curcuma,sappanwood, cochineal, logwood, henna, Castanea (chestnut tree), Alliumcepa (onion) or coffee, an extract thereof, a powder obtained byfreeze-drying the extract, and a mixture thereof.

The hair dye according to the fifth aspect of the present invention canprovide widened variation in colors, since it contains other dyematerials as described above.

A sixth aspect of the present invention is characterized in that, theforegoing hair dye further comprises, as a bulking filler or as anexcipient, a plant-based component derived from a plant selected fromthe group consisting of a tea leaf, comfrey, kamille, chlorella,rosemary, seaweed, and a mixture thereof.

The hair dye according to the sixth aspect of the present invention canprovide an increased quantity by adding a plant-based component asdescribed above.

A seventh aspect of the present invention is characterized in that, theforegoing hair dye further comprises, as a hair-dyeing conditioner, asaponin-containing plant-based component selected from the groupconsisting of Sappindus Mukurossi Gaertn., Gleditschia Japonica Mig.,Quillaia Saponaria Molina and a mixture thereof.

The hair dye according to the seventh aspect of the present inventioncan suppress the formation of indirubin to allow the expression of thenatural indigo color, since it contains, as a hair-dyeing conditioner,saponin-containing plant-based components as described above. One canpursue widened variation of colors, such as reddish purple added to thenatural indigo color, by choosing the kinds of the saponin-containingplants used and by varying their amounts to be added.

An eighth aspect of the present invention is characterized in that, theforegoing hair dye further comprises a plant-based thickener includingguar gum and purified extracts of seaweed, or an animal-based thickenerincluding a silk protein in order to enhance the adhesive power to hairas well as the ability in hair-dyeing operation.

The hair dye according to the eighth aspect of the present invention hasan advantage that, since the dye contains plant-based thickeners asdescribed above, the dye can be conditioned so that it adheres well tohair, preventing the dye from dripping down when applied to hair. Thisimproves the ability in hair-dyeing operation.

A ninth aspect of the present invention is characterized in that, theforegoing hair dye further comprises a naturally occurring or chemicallysynthesized additive including an oil, a conditioner, a surfactant, ahumectant, and a mixture thereof, in order to provide hair with anenhanced texture.

The hair dye according to the ninth aspect of the present invention canprovide hair with an enhanced texture, since the hair dye containsnaturally occurring or chemically synthesized additives as describedabove.

A tenth aspect of the present invention is characterized in that, theforegoing hair dye further comprises an additive selected from the groupconsisting of an antiseptic or germicide such as parabens and benzoates,an anti-oxidant, a UV-absorbing agent, a chelating agent, and a mixturethereof, in order to achieve improved long-term stability.

The hair dye according to the tenth aspect of the present invention canachieve improved long-term stability, since the dye contains additivesas described above.

An eleventh aspect of the present invention is a hair-dyeing methodcomprising the steps of: mordanting hair with a dye mordant selectedfrom the group consisting of a metal element of aluminum, iron, zinc,nickel, calcium, or magnesium, a metal salt thereof, and a mixturethereof; uniformly applying any of the foregoing hair dyes, theafore-mentioned hair dye comprising the formulation (i) primarilycomposed of the dye component including the indican derived from anindigo plant and the formulation (ii) primarily composed of theβ-glucosidase enzyme component, the hair dye being applied to haireither directly or after mixed with a proper amount of water; and, uponcompletion of hair-dyeing, finishing the hair by rinsing with water anddrying.

The method according to the eleventh aspect of the present inventionensures firm dyeing of hair.

A twelfth aspect of the present invention is a hair-dyeing methodcomprising the steps of: uniformly applying any of the foregoing hairdyes, the afore-mentioned hair dye comprising the formulation (i)primarily composed of the dye component including the indican derivedfrom indigo plants and the formulation (ii) primarily composed of theβ-glucosidase enzyme component, the hair dye being applied eitherdirectly or after mixed with a proper amount of water; upon completionof hair-dyeing, mordanting hair with a dye mordant selected from thegroup consisting of a metal element of aluminum, iron, zinc, nickel,calcium, or magnesium, a metal salt thereof, and a mixture thereof; andfinishing the hair by rinsing with water and drying.

The method according to the twelfth aspect of the present inventionensures firm dyeing of hair.

BRIEF DESCRIPTION OF THE DRAWING

FIGURE illustrates the principle of color expression in hair-dyeingusing indigo plants.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention will now be described in detail with reference tothe accompanying drawing.

Examples of the plant from which indigo dyestuff of the presentinvention is made include, but are not limited to, those belonging tothe genus indigofera including Polygonum tinctorium, Strobilanthescusia, Indigofera tinctoria, and Isatis indigotica.

Polygonum tinctorium LOUR is an annual plant which belongs to the familyPolygonaceae and is found in Indonesia, China and Japan.

Strobilanthes cusia (NEES) is a perennial plant belonging to the familyAcanthaceae and is found in China and Okinawa.

Indigofera tinctoria is a perennial plant belonging to the familyLeguminosae. It grows in countries such as India and Java.

Isatis indigotica FORTUNE is an annual plant belonging to the familyCurciferae, and grows in the middle Europe and China.

Preferably, leaves of the indigo plants are used although the wholeplant including roots and stems may also be used. The top leaves ingrowth are particularly suitable for use, though the leaves harvestedfor the first time or the third time of the year may also be used.

The figure shows the principle of how colors are expressed inhair-dyeing using the indigo plants.

As shown in the figure, indican (1) (water-soluble), which is aglucoside contained in the indigo plants principally in their leaves, ishydrolyzed by β-glucosidase, an enzyme which co-exists with the indicanin the same plant, to form indoxyl (2) (water-soluble). The indoxyl (2)undergoes an oxidative dimerization to form indigo (3)(water-insoluble), which expresses colors.

For example, when a juice obtained by squeezing fresh indigo leaves isimmediately applied to hair, hair-dyeing is accomplished in thefollowing manner: Since the juice of fresh indigo leaves contains bothindican (1) and the enzyme (β-glucosidase), indican (1) is hydrolyzed bythe enzyme (β-glucosidase) to form indoxyl (2). The resulting indoxyl(2) penetrates into hair. When exposed to air, indoxyl (2) is oxidizedand dimerizes to form indigo (3). This dyes the hair.

A drawback of this approach is that the chemical reaction as describedabove may proceed while the juice of indigo fresh leaves is stored,since the juice contains both indican (1) and the enzyme(β-glucosidase). This leads to reduced long-term stability.

The present invention is based on the discovery that the undesirableproceeding of the above-described reaction while the juice is stored canbe avoided, for example, by separating (i) a dye component includingindigo plant-derived indican, and (ii) an enzyme component, i.e.,β-glucosidase, from the juice of fresh indigo leaves containing indican(1) and the enzyme (β-glucosidase), and then making each component intoan individual formulation so that the two formulations are mixedtogether upon use to dye hair.

In the present invention, Examples of the formulation primarily composedof the dye component (i) including indican (1) derived from indigoplants include fresh indigo leaves in which the enzyme (β-glucosidase)is inactivated, or indican-containing extracts extracted from freshindigo leaves in which the enzyme (β-glucosidase) is inactivated.

The enzyme (β-glucosidase) may be inactivated by heat-treating the freshindigo leaves or the juice thereof, which contain the enzyme(β-glucosidase), for example, at a temperature from 60° C. to 100° C.for 3 to 60 minutes.

Fresh indigo leaves having the enzyme (β-glucosidase) inactivated mayeasily be obtained by heat-treating or steaming the fresh indigo leaveswith the above-mentioned heat-treating conditions, by treating theleaves in a microwave, or by drying the leaves by sunlight.

Indican-containing extracts having the enzyme (β-glucosidase)inactivated may be obtained by extracting it from fresh indigo leaves inwarm water in the temperature range mentioned above, or boiling,steaming, or microwaving the juice containing the enzyme (β-glucosidase)extracted from fresh indigo leaves in cold water, in the aforementionedtemperature range.

In the present invention, the formulation primarily composed of the dyecomponent (i) containing indican derived from indigo plants may beformed as an indican-containing powder obtained by freeze-drying, by aconventional method, the aforementioned indican-containing extractshaving the enzyme (β-glucosidase) inactivated. Making the formulationinto a powder is preferred since it ensures high shelf stability andeasy-handling.

Also, in the present invention, the formulation primarily composed ofthe dye component (i) containing indican derived from indigo plants maybe an indican-containing formulation in which the above-described freshindigo leaves having the enzyme (β-glucosidase) inactivated, and/or, theabove-described indican-containing extracts having the enzyme(β-glucosidase) inactivated, and/or, the above-descrivedindican-containing powder having the enzyme (β-glucosidase) inactivatedis/are carried on a carrier such as starch, cellulose, silk powder.

Further, the formulation primarily composed of the dye component (i)containing indican derived from indigo plants may be formed as anindican-containing powder obtained by freeze-drying the aforementionedindican-containing extracts, which have the enzyme (β-glucosidase)inactivated and which is carried on a carrier such as starch, cellulose,silk powder or the like.

In the present invention, Examples the formulation primarily composed ofthe β-glucosidase enzyme component (ii) are not limited to those derivedfrom indigo plants but includes those derived from Enokitake (Flammulinavelutipes), Shiitake (Lentinus Edodes), young corn leaves, apricotkernels, almonds and the like, or β-glucosidase-containing extractsextracted therefrom.

In the present invention, however, the formulation primarily composed ofthe β-glucosidase enzyme component (ii) is preferably fresh indigoleaves or a juice thereof, or a β-glucosidase-containing powder obtainedby freeze-drying fresh indigo leaves or a juice thereof.

Fresh indigo leaves or a juice of the fresh indigo leaves may be used asthe above-described formulation primarily composed of β-glucosidaseenzyme component (ii) since they contain both indican (1) and the enzyme(β-glucosidase), as described above.

In case of the fresh indigo leaves, the indican (1) present in theleaves would not be hydrolyzed by the enzyme (β-glucosidase) unless theleaves are beaten or smashed, while the juice of the fresh indigo leavesis susceptible to hydrolysis by the enzyme (β-glucosidase). Therefore,the juice of the fresh indigo leaves is preferably used by freeze-dryingit into an enzyme (β-glucosidase) containing powder by a known method.The indican (1) in the enzyme (β-glucosidase) containing powder is nothydrolyzed by the enzyme (β-glucosidase) since no water is present inthe powder. This ensures high shelf stability.

The formulation composed primarily of the dye component (i) includingthe indican derived from indigo plants, or the formulation composedprimarily of the β-glucosidase enzyme component (ii) is preferablyencapsulated in bags made of a multi-layered plastic film impermeable towater and oxygen or in glass containers, for the purposes of storage andtransportation. The encapsulated formulations are stored until use whenthe seal is broken.

When the hair dye according to the present invention is used to dyehair, the formulation composed primarily of the dye component (i)including the indican derived from indigo plants and the formulationcomposed primarily of the β-glucosidase enzyme component (ii) are mixedto be uniformly applied to hair. The mixture may be applied directlyonto hair, or alternatively, the mixture may further be mixed with aproper amount of water for application. Indican (1) is hydrolized by theenzyme (β-glucosidase) to form indoxyl (2). The resulting indoxyl (2)penetrates into hair. When exposed to air, the indoxyl (2) is oxidizedand dimerizes to form indigo (3). Not only does this enable to dye hairin a desired dark color but also ensures highly durable hair-dyeing.After dyeing is completed, the hair is rinsed with water and is finishedby drying.

The hair dye according to the present invention may be used alone, oranother hair dyeing material may preferably be added to providevariation in colors.

Examples of the other hair dyeing material include gamene, Quercusglauca, Prunus armeniaca (apricot), Rubia muneet, curcuma, Prunus mume(plum), Sophora japonica, Bruguiera gymnorriza, Diospyros kaki, Quercusdentata, Arthraxon hispidus, Chaenomeles sinensis, gambier,Phellodendron amurense, Osmanthus fragrans var. aurantiacus,Clerodendoron trichotomum, Cinnamonum camphora, Gardenia jasminoides,Quercus acutissima, Castanea (chestnut tree), Phyllostachys nigera var.nigera, Morus, Zelkova serrata, Laurus nobilis, Geranium nepalensesubsp. thunbergii, tea, coffee, cochineal, Quercus serrata, Japanesegall (Melaphis chinensis), Viburnum erosum, Arthraxon hispidus, Prunus(cherry), Punica granatum, Chrysanthemum coronarium, Shirakashi(Japanese name), sappanwood, Malus sieboldii, Rubia tinctorum, Ilexpedunculosa, Machilus tunbergii, Allium cepa (onion), Daphne genkwa,Houttuynia cordata, Japanese cinnamon, Cornus florida, Erigeronphiladelphicus, Arachis hypogea (peanut), Eribotrya japonica, Arecacatechu, Pegucatechu, Carthamus tinctorius, Tagetes erecta (Marigold),Cornus controversa, myrobalan, Aphananthe aspera, gromwell(Boraginaceae), Alnus firma Sieb. et Zucc., Boehmeria longispica, Cornuskousa, Myrica rubra, Artemisia princeps, lac, green tea, logwood, andmixtures of more than two of them.

Of these, natural plant dyes of gamene, curcuma, sappanwood, cochineal,logwood, henna, Castanea (chestnut tree), Allium cepa (onion), andcoffee may preferably be used.

Dried and powdered portion of these plants including roots, stems,skins, leaves, flowers, fruits and seeds may be used. Also, an extractsolution extracted using proper solvent or powdered extract maypreferably be used. Examples of the solvent include water, alcoholshaving 6 carbons or less, polyols, benzene, chloroform, acetone, andethers. These solvents may be used either individually or in combinationof more than two.

Also, a plant-based component derived from plants such as aloe, kamille,licorice, chlorella, comfrey, cinnamon, shiitake, jasmine, sage, carrot,garlic, tea, peppermint, Marigold, lavender, rosemary, and seaweeds maybe added in a proper amount as a bulking filler or an excipient.

Among these plants, tea leaves, comfrey, kamille, chlorella, rosemary,or seaweed is preferably used.

Furthermore, a saponin-containing plant including Sappindus MukurossiGaertn., Gleditschia Japonica Mig., Quillaia Saponaria Molina, Panaxginseng, Panax ginseng var. japonica, Platycodon grandiflorum (Chinesebellflower), Aralia elata, Sophora japonica, senega, Glycine max(Soybean), licorice, or Fatsia japonica may be added to the hair dye ofthe present invention as a hair-dyeing conditioner.

As shown in the figure, in addition to the reaction pathway in whichindican (1) is hydrolyzed by the enzyme (β-glucosidase) to form indoxyl(2) (water-soluble) which oxdatively dimerizes to form indigo (3) whenexposed to air, there is another pathway in which indirubin (5) isformed via isatin (4). The amount of indirubin (5) produced may beincreased depending on conditions under which hair is dyed. Sinceindirubin (5) has a reddish purple color, this may cause the blue ordeep-blue color, which is the natural color of indigo, to diminish,making hair appear more reddish purple.

However, because the addition of the saponin-containing plant such asSappindus Mukurossi Gaertn., Gleditschia Japonica Mig., QuillaiaSaponaria Molina to the hair dye of the present invention can suppressthe formation of indirubin (5) and hence increase the amount of indigo(3) produced, natural colors of indigo plants are well expressed.

Accordingly, when it is desired to dye hair in the natural colors ofindigo plants, it is preferred to add the saponin-containing plant suchas Sappindus Mukurossi Gaertn., Gleditschia Japonica Mig., or QuillaiaSaponaria Molina, preferably, Sappindus Mukurossi Gaertn. The naturalcolors of indigo plants may be adjusted to a slightly reddish purpledepending on the kind of the saponin-containing plant or the amount ofthe plant added. Also, it is possible to obtain widened variation incolor.

Sappindus Mukurossi Gaertn. has long been used as a detergent and isknown to have a strong ability to foam. Hence, the plant is believed toact to provide a large surface area due to the formation of bubbles andthus a large supply of air. This may enhance the oxidative reaction inwhich indoxyl (2) oxidatively dimerizes to form indigo (3).

The amount of the above-described saponin-containing plant added is notparticularly limited, but typically in a range from 0.1 to 20.0 wt %,preferably from 1 to 5 wt %, with respect to the total amount of thehair dye. When the amount is less than 0.1 wt %, suppression offormation of indirubin (5) is low. When the amount is greater than 20.0wt %, further increases in the suppression effect are hardly expected.Rather, the hair-dyeing performance may deteriorate.

A thickener may be added in a proper amount to the hair dye of thepresent invention in order to enhance the adhesive power to hair as wellas the ability in hair-dyeing operation.

Examples of the thickener include a) natural, semi-synthesized, orsynthesized water-soluble polymers, b) electrolytes such as sodiumchloride, potassium chloride, and sodium sulfate, c) nonionicsurfactants, and d) oils.

In the present invention, a plant-based thickener including guar gum andpurified extracts of seaweed, or animal-based thickeners including silkproteins is preferably used.

Examples of the other thickeners which may be used in the presentinvention include thickeners composed of those selected from the groupconsisting of celluloses, alginates and polysaccharides, and inparticular, one or a mixture of more than two thickeners selected fromthe group consisting of methyl celluloses, ethyl celluloses,hydroxyethyl celluloses, methylhydroxyethyl celluloses,methylhydroxypropyl celluloses, carboxymethyl celluloses,polyvinylalcohol, carboxy vinyl polymers, alginic acid, sodium alginate,ammonium alginate, calcium alginate, gum arabic, xanthan gum,carrageenan, and cationic derivatives thereof. Preferably, the amount ofthe thickener to be added is from about 0.1 to about 15 wt %, and inparticular, from about 0.2 to about 10 wt %.

Also, naturally occurring or chemically synthesized additives includingoils, conditioners, surfactants and humectants may be added in a properamount to the hair dye of the present invention in order to bettertexturize hair.

Examples of the additive which may used in the present invention includeanimal or plant-based fats and oils such as lanolin, mink oil, horseoil, almond oil, castor oil, jojoba oil, medford oil, and olive oil;animal or plant-based sterols such as cholesterin, lanolin alcohol,phytosterols and derivatives thereof; mineral, animal or plant-basedwaxes such as solid paraffin, ceresin, spermaceti wax, beewax, andcarnauba wax; hydrocarbon oils such as liquid paraffin and squarane;higher alcohols such as lauryl alcohol, cetanol, cetostearil alcohol,and oleyl alcohol; higher fatty acids such as lauric acid, stearic acid,and oleic acid; synthetic oils such as polyoxyethylene polyoxypropyleneglycol, isopropyl myristate, isopropyl palmitate, cetostearil isooctate,alkyl esters of isostearic acid; surfactants such aspolyoxyethylenealkylether sulfate,2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, andN-coconut fatty acid acyl-L-glutamate; surfactants such as higheralcohol polyoxyethylene ethers, higher fatty acid polyoxyethyleneesters, hardened castor oil polyoxyethylene; polyols such as glycerol,sorbit, propylene glycol, 1,3-butylene glycol; lower alcohols such asethanol; moisturizers such as hyaluronates, pyrrolidone carboxylate,hydrolyzed collagen, hydrolyzed keratin, hydrolyzed silk, and trehalose;and cationizing agents such as alkyltrimethylammonium chloride andcationized dextran.

The conditioner is added for the purposes of 1) preventing frizzy hairto assure smooth combing, 2) always keeping hair moist and soft for easytaming and long-lasting curls, 3) adding body and shine to hair, and 4)strengthening the hair.

Further additive selected from a germicide and/or an antiseptic such asparabens and benzoates, an anti-oxidant, a UV-absorbing agent, and achelating agent may be added to the hair dye of the present invention inan proper amount that does not affect the desired effects of the hairdye of the present invention. The amount of the additive to be added isnot limitative, but preferably in a range from 0.01 to 1.0 wt % withrespect to the total amount of the hair dye. When the amount is lessthan 0.01 wt %, the long-term stability may not be obtained. Conversely,further improvement in the long-term stability is hardly expected andthe hair dye may become costly when the amount exceeds 1.0 wt %.

Examples of the germicide and antiseptic which may be used in thepresent invention include acids such as benzoic acid, salicylic acid,dehydroacetic acid, and sorbic acid and salts thereof, sodium banzoate,oxybenzoic acid alkyl esters, cetylpyridinium chloride, benzalkoniumchloride, alkyltrimethylammonium chloride, phenoxyethanol, triclosan,trichloro carbanilide, zinc pyrithione, and ethanol. Typically, use oftwo or more germicides or antiseptics in combination is effective.

Examples of the chelating agent (metal blocking agent) which may be usedin the present invention include ethylenediaminetetraacetic acidderivatives, tripolyphosphate, hexametaphosphate, dihydroxyethylglycine,citric acid, tartaric acid, gluconic acid, and sugar acid. These agentsact by forming complex salts with trace amounts of heavy metal ions.

Examples of the UV absorbing agent which may be used in the presentinvention include benzophenone derivatives such as oxybenzon, andbenzatriazol derivatives.

The anti-oxidant used in the present invention is intended forpreventing the hair dyes and hair dye compositions of the presentinvention from being oxidized. Examples of the anti-oxidant used hereinincluding tocophenol, nordihydroguaiaretic acid, butylhydroxyanisole,dibutylhydroxytoluene, propyl gallate, sodium hydrogensulfite,erythorbic acid, parahydroxyanisole, extracts of tea, and extracts ofapples may be used for this purpose.

A proper amount of perfumery may be added to the hair dye of the presentinvention. Perfumery is an important ingredient which, as well ascolors, contributes to the products' attractiveness and increases thecommodity values. It is also important in masking unpleasant odor ofother ingredients.

One method for dyeing hair using the hair dye of the present inventionincludes first mordanting hair with a dye mordant including a metalelement such as aluminum, iron, zinc, nickel, calcium and magnesium, ora metal salt thereof, and then uniformly applying the hair dye includingthe formulation primarily composed of the dye component (i) includingthe indican derived from indigo plants and the formulation primarilycomposed of the β-glucosidase enzyme component (ii). The formulationsmay be applied either directly or after mixed with a proper amount ofwater (for example, 10 to 200 g of water are mixed with 1 to 50 g of amixture of the formulations (i) and (ii), and preferably, 50 to 150 g ofwater are mixed with 5 to 30 g of a mixture of the formulations (i) and(ii).) Hair-dyeing conditions are not particularly limited, but forexample, hair-dyeing is carried out by leaving the hair for several to30 minutes at about 40 to 45° C. After hair-dyeing is completed, thehair is rinsed with water and is finished by drying. Application of thedye mordant prior to the application of the hair dye provides moredurable dyeing as compared to the hair-dyeing without thepre-application of the dye mordant.

Another method for dyeing hair using the hair dye of the presentinvention includes uniformly applying the hair dye including theformulation primarily composed of the dye component (i) including theindican derived from indigo plants and the formulation primarilycomposed of the β-glucosidase enzyme component (ii). The formulationsmay be applied either directly or after mixed with a proper amount ofwater (for example, 10 to 200 g of water are mixed with 1 to 50 g of amixture of the formulations (i) and (ii), and preferably, 50 to 150 g ofwater are mixed with 5 to 30 g of a mixture of the formulations (i) and(ii).) Hair-dyeing conditions are not particularly limited, but forexample, hair-dyeing is carried out by leaving the hair for several to30 minutes at about 40 to 45° C. Upon completion of hair-dyeing, thehair is treated with a dye mordant including a metal element such asaluminum, iron, zinc, nickel, calcium or magnesium, or a metal saltthereof.

Subsequently, the hair is rinsed with water and is finished by drying.Application of the dye mordant after the application of the hair dyeprovides more durable dyeing as compared to the hair-dyeing without thepost-application of the dye mordant.

EXAMPLES

The present invention will now be described in further detail, however,it should be appreciated that the present invention is not limited tothese examples.

Example 1

Fresh indigo leaves collected from the top portion of the growing indigoplants were extracted in hot water at a temperature of about 80 to 90°C. for about 10 to 20 minutes to prepare an extract solution in whichthe enzyme (β-glucosidase) had been inactivated. As a carrier, acellulose powder was used to carry the extract, and the extract carriedby the cellulose powder was freeze-dried to obtain an indican-containingformulation. A β-glucosidase-containing powder (i.e., enzyme(β-glucosidase) containing formulation) was prepared by freeze-dryingcrushed fresh indigo leaves. A hair dye according to the presentinvention was prepared by mixing 10.0 g of the indican-containingformulation, 1.0 g of the enzyme (β-glucosidase) containing powder, and1.0 g of powdered extracts of Sappindus Mukurossi Gaertn. and dissolvingthe mixture into 100 ml of purified water. The dye was applied to hair,which was then wrapped in an appropriate manner, warmed to about 40 to45° C. and left for 30 minutes. The hair was then dried and finished.

The hair dye of the present invention did not cause irritation or damageto scalps and hair, nor did it stain skins when spilt. Furthermore, thehair dye of the present invention was capable of preventing white hairfrom turning yellowish color and of dyeing hair with natural tone. Italso showed high durability and provided hair with a new texture. Theaddition of the powdered extracts of Sappindus Mukurossi Gaertn.provided a darker blue.

Example 2

Fresh indigo leaves collected from the top portion of the growing indigoplants was extracted in hot water at a temperature of about 80 to 90° C.for about 10 to 20 minutes to prepare an extract solution in which theenzyme (β-glucosidase) had been inactivated. As a carrier, a cellulosepowder was used to carry the extract, and the extract carried by thecellulose powder was freeze-dried to obtain an indican-containingformulation.

A β-glucosidase-containing powder (i.e., enzyme (β-glucosidase)containing formulation) was prepared by freeze-drying crushed freshindigo leaves. A hair dye according to the present invention wasprepared by mixing 10.0 g of the indican-containing formulation, 1.0 gof the enzyme (β-glucosidase)containing powder, 1.0 g of powderedextracts of Sappindus Mukurossi Gaertn., and 1.4 g of guar gum, anddissolving the mixture into 100 ml of purified water. The dye wasapplied to hair, which was then wrapped in an appropriate manner, warmedto about 40 to 45° C. and left for 30 minutes. The hair was then driedand finished.

The hair dye of the present invention did not cause irritation or damageto scalps and hair, nor did it stain skins when spilt. Furthermore, thehair dye of the present invention was capable of preventing white hairfrom turning yellowish color and of dyeing hair with natural tone. Italso showed high durability and provided hair with a new texture. Theaddition of the guar gum enhanced the applicability of the dye andprevented the hair dye from dripping down.

Example 3

Hair-dyeing was carried out in the same manner as in Example 2 exceptthat 5.0 g of powdered curcuma were used as an further additive.

The hair dye of the present invention did not cause irritation or damageto scalps and hair, nor did it stain skins when spilt. Furthermore, thehair dye of the present invention was capable of preventing white hairfrom turning yellowish color and of dyeing hair with natural tone. Italso showed high durability and provided hair with a new texture. Theaddition of the powdered curcuma provided widened variation in color: Ayellowish tone was added to the bluish tone, producing a greenish tone.

Example 4

Hair-dyeing was carried out in the same manner as in Example 3 exceptthat 5.0 g of powdered henna were used in place of the powdered curcuma.

The hair dye of the present invention did not cause irritation or damageto scalps and hair, nor did it stain skins when spilt. Furthermore, thehair dye of the present invention was capable of preventing white hairfrom turning yellowish color and of dyeing hair with natural tone. Italso showed high durability and provided hair with a new texture. Theaddition of the powdered henna provided widened variation in color: Anorangeish tone was added to the bluish tone, producing a brownish tone.

Example 5

Hair-dyeing was carried out in the same manner as in Example 2 exceptthat 3.0 g of powdered kamille were used as an further additive.

The hair dye of the present invention did not cause irritation or damageto scalps and hair, nor did it stain skins when spilt. Furthermore, thehair dye of the present invention was capable of preventing white hairfrom turning yellowish color and of dyeing hair with natural tone. Italso showed high durability and provided hair with a new texture. Theaddition of the powdered kamille produced a grayish blue and provided anenhanced touch of the hair.

Example 6

Hair-dyeing was carried out in the same manner as in Example 2 exceptthat 3.0 g of powdered seaweed were used as an further additive.

The hair dye of the present invention did not cause irritation or damageto scalps and hair, nor did it stain skins when spilt. Furthermore, thehair dye of the present invention was capable of preventing white hairfrom turning yellowish color and of dyeing hair with natural tone. Italso showed high durability and provided hair with a new texture. Theaddition of the powdered seaweed provided enhanced shine and touchwithout sacrificing the indigo color.

Example 7

Hair-dyeing was carried out in the same manner as in Example 2 exceptthat 3.0 g of powdered keratin were used as an further additive.

The hair dye of the present invention did not cause irritation or damageto scalps and hair, nor did it stain skins when spilt. Furthermore, thehair dye of the present invention was capable of preventing white hairfrom turning yellowish color and of dyeing hair with natural tone. Italso showed high durability and provided hair with a new texture. Theaddition of the powdered keratin provided an increased resiliency aswell as enhanced shine and touch without sacrificing the indigo color.

Example 8

Hair-dyeing was carried out in the same manner as in Example 2 exceptthat 3.0 g of powdered silk were used as an further additive.

The hair dye of the present invention did not cause irritation or damageto scalps and hair, nor did it stain skins when spilt. Furthermore, thehair dye of the present invention was capable of preventing white hairfrom turning yellowish color and of dyeing hair with natural tone. Italso showed high durability and provided hair with a new texture. Theaddition of the powdered silk provided an increased slip as well asenhanced shine and touch without sacrificing the indigo color.

In view of the results obtained by the Examples 5-8, it was determinedthat an enhanced touch of the dyed hair could be obtained by adding theadditives such as a powdered plant, a hydrolyzed protein and the like.

While the presently preferred embodiments of the present invention havebeen shown and described, it will be understood that the presentinvention is not limited thereto, and that various changes andmodifications may be made by those skilled in the art without departingfrom the scope of the invention as set forth in the appended claims.

What is claimed is:
 1. A hair dye comprising, as essential ingredients,(i) a formulation composed of a dye component including an indican whichis derived from an indigo plant and has been heat-treated to inactivatethe natural β-glucosidase contained therein and (ii) a formulationcomposed of a β-glucosidase enzyme component.
 2. The hair dye accordingto claim 1, wherein said formulation (i) composed of the dye componentincluding indican is selected from the group consisting of a freshindigo leaf which has been heat-treated to inactivate the naturalβ-glucosidase contained therein; an extract solution which containsindican extracted from fresh indigo leaves and has been heat-treated toinactivate the natural β-glucosidase contained therein; anindican-containing powder obtained by freeze-drying anindican-containing extract solution; an indican-containing formulationin which the fresh indigo leaves have been heat-treated to inactivatethe natural β-glucosidase contained therein; an indican-containingextract solution; an indican-containing powder carried by a carrierselected from the group consisting of starch, cellulose, and silkpowder; and mixtures thereof.
 3. The hair dye according to claim 1,wherein said β-glucosidase enzyme component is selected from the groupconsisting of extract of a fresh indigo leaf, Enokitake (Flammulinavelutipes), Shitake (Lentinus Edodes), a young corn leaf, an apricotkernel, an almond, and mixtures thereof.
 4. The hair dye according toclaim 1, wherein the formulation (ii) composed of the β-glucosidaseenzyme component is one selected from the group consisting of a juice ofa fresh indigo leaf, a β-glucosidase-containing powder obtained fromfreeze-dried fresh indigo leaves or juice thereof, and mixtures thereof.5. The hair dye according to claim 1, further comprising another dyematerial selected from the group consisting of a natural plant dyestuffof gamene, curcuma, sappanwood, cochineal, logwood, henna, Castanea(chestnut tree), Allium cepa (onion) or coffee, an extract thereof, apowder obtained by freeze-drying the extract, and a mixture thereof. 6.The hair dye according to claim 1, further comprising, as a bulkingfiller or as an excipient, a plant-based component derived from a plantselected from the group consisting of a tea leaf, comfrey, kamille,chlorella, rosemary, seaweed, and a mixture thereof.
 7. The hair dyeaccording to claim 1, further comprising, as a hair-dyeing conditioner,a saponin-containing plant-based component selected from the groupconsisting of Sappindus Mukurossi Gaertn., Gleditschia Japonica Mig.,Quillaia Saponaria Molina and a mixture thereof.
 8. The hair dyeaccording to claim 1, further comprising a plant-based thickenerincluding guar gum and purified extracts of seaweed, or an animal-basedthickener including a silk protein in order to enhance the adhesivepower to hair as well as the ability in hair-dyeing operation.
 9. Thehair dye according to claim 1, further comprising a naturally occurringor chemically synthesized additive including an oil, a conditioner, asurfactant, a humectant, and a mixture thereof, in order to provide hairwith an enhanced texture.
 10. The hair dye according to claim 1, furthercomprising an additive selected from the group consisting of anantiseptic or germicide such as parabens and benzoates, an anti-oxidant,a UV-absorbing agent, a chelating agent, and a mixture thereof, in orderto achieve improved long-term stability.
 11. The hair dye according toclaim 2, wherein: the formulation (ii) composed of the β-glucosidaseenzyme component is one seleted from the group consisting of extract ofa fresh indigo leaf, Enokitake (Flammulina velutipes), Shitake (LentinusEdodes), a young corn leaf, an apricot kernel, an almond, and mixturesthereof; and further comprising: another dye material selected from thegroup consisting of a natural plant dyestuff of gamene, curcuma,sappanwood, cochineal, logwood, henna, Castanea (chestnut tree), Alliumcepa (onion) or coffee, an extract thereof, a powder obtained byfreeze-drying the extract, and mixtures thereof; as a bulking filler oras an excipient, a plant-based component derived from a plant selectedfrom the group consisting of a tea leaf, comfrey, kamille, chlorella,rosemary, seaweed, and a mixture thereof; as a hair-dyeing conditioner,a saponin-containing plant-based component selected from the. groupconsisting of Sappindus Mukurossi Gaertn., Gleditschia Japonica Mig.,Quillaia Saponaria Molina and a mixture thereof; a plant-based thickenerselected from the group consisting of guar gum and purified extracts ofseaweed, or an animal-based thickener in order to enhance the adhesivepower to hair as well as the ability in hair-dyeing operation; anaturally occurring or chemically synthesized additive selected from thegroup consisting of an oil, a conditioner, a surfactant, a humectant,and a mixture thereof, in order to provide hair with an enhancedtexture; an additive selected from the group consisting of an antisepticor germicide, an anti-oxidant, a UV-absorbing agent, a chelating agent,and a mixture thereof, in order to achieve improved long-term stability.12. The hair dye according to claim 2, wherein: the formulation (ii)composed of the β-glucosidase enzyme component is one selected from thegroup consisting of a juice of a fresh indigo leaf, aβ-glucosidase-containing powder obtained by freeze-dried fresh indigoleaves or juice thereof, and a mixture thereof; and further comprising:another dye material selected from the group consisting of a naturalplant dyestuff of gamene, curcuma, sappanwood, cochineal, logwood,henna, Castanea (chestnut tree), Allium cepa (onion) or coffee, anextract thereof, a powder obtained by freeze-drying the extract, and amixture thereof; as a bulking filler or as an excipient, a plant-basedcomponent derived from a plant selected from the group consisting of atea leaf, comfrey, kamille, chlorella, rosemary, seaweed, and a mixturethereof; as a hair-dyeing conditioner, a saponin-containing plant-basedcomponent selected from the group consisting of Sappindus MukurossiGaertn., Gleditschia Japonica Mig., Quillaia Saponaria Molina and amixture thereof; a plant-based thickener selected from the groupconsisting of guar gum and purified extracts of seaweed, or ananimal-based thickener in order to enhance the adhesive power to hair aswell as the ability in hair-dyeing operation: a naturally occurring orchemically synthesized additive selected from the group consisting of anoil, a conditioner, a surfactant, a humectant, and a mixture thereof, inorder to provide hair with an enhanced texture; an additive selectedfrom the group consisting of an antiseptic or germicide, ananti-oxidant, a UV-absorbing agent, a chelating agent, and a mixturethereof, in order to achieve improved long-term stability.
 13. The hairdye of claim 11 wherein said thickener is a silk protein.
 14. The hairdye of claim 11 wherein said germicide is a parabens compound or abenzoate.
 15. The hair dye of claim 12 wherein said thickener is a silkprotein.
 16. The hair dye of claim 12 wherein said germicide is aparabens compound or a benzoate.